WO2005061646A1 - Adhesion promoters for sealants - Google Patents
Adhesion promoters for sealants Download PDFInfo
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- WO2005061646A1 WO2005061646A1 PCT/US2003/036990 US0336990W WO2005061646A1 WO 2005061646 A1 WO2005061646 A1 WO 2005061646A1 US 0336990 W US0336990 W US 0336990W WO 2005061646 A1 WO2005061646 A1 WO 2005061646A1
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- sealant composition
- carbon
- branched
- straight chain
- saturated
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- 0 C*C(C(*)C(C1C)*(O*)=O)C2C1C(C)C=CC2* Chemical compound C*C(C(*)C(C1C)*(O*)=O)C2C1C(C)C=CC2* 0.000 description 5
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/04—Non-macromolecular organic compounds
- C09K2200/0441—Carboxylic acids, salts, anhydrides or esters thereof
Definitions
- the esters provide unexpected, tenacious bonding between the sealants and the substrate, when combined with an adhesive resin. It is theorized that the long chain esters of the invention strongly adhere both to the sealant composition and to the resin, with the resin providing sufficient bonding to the substrate.
- suitable substrates include metal surfaces such as steel surfaces, brass-coated steel surfaces, copper surfaces, brass surfaces and aluminum surfaces, glass surfaces, polymeric surfaces, cementitious surfaces such as concrete, asphaltic surfaces, and the like.
- sealant compositions characterized by good adhesion to various substrates.
- Another aspect of the invention provides methods of adhering a sealant composition to a substrate.
- adheresion promoter system refers to the combination of at least one long chain ester compound and at least one adhesive resin.
- the adhesion promoter systems of the invention are useful for improving the adhesion of sealant compositions to various substrates, particularly ceramic substrates such as concrete.
- the curing agent After application of the sealant (or a sealant composition in accordance with the invention) to a substrate, the curing agent causes cross-linkages to form between the polymers, typically resulting in the in-situ formation of a cross-linked/branched polymeric material having an elastomeric-like consistency.
- waterborne sealants can include high molecular weight polymers, which are encapsulated in emulsion form, which allows for ease of flow for application to substrates. In such an emulsion sealant, a curing agent is typically not needed for development of desired physical properties.
- Most sealants comprise synthetic polymers; however, sealants including natural polymers are also known.
- Urethane sealants Polymer: reaction product of an amine or alcohol functionalized polyether with a diisocyanate. Curing agent: diisocyanates. Additives: plasticizers, UN absorbers, dibutylphthalate, dibenzylphthalate, butylbenzylphthalate, carbon black, titanium dioxide. Fillers: calcium carbonate. Conventionally known adhesion promoters: amino functionalized silanes. 5. Modified urethane sealants Polymer: reaction product of a polyether, a diisocyanate and an amino functionalized silane or alkoxysilane terminated polyether. Curing agent: alkoxy functionalized silanes (methyltrimethoxysilane, etc).
- the inventive sealant compositions provide excellent adhesion to ceramic, glass, metal and polymeric substrates, and can be used to seal in and around bathroom fixtures, in storage areas, in vents, plumbing lines, flooring, vehicular wheel wells, sanitary and storm sewer manholes, irrigation and drainage system joints, septic tanks, underground vault seals (e.g., burial vaults), architectural foundation joints, in conjunction with o-rings (for example, in pipe joints), and the like.
- the sealant compositions in accordance with the invention are surprisingly weather-resistant, and therefore provide sealing and bonding products capable of use in the manufacturing and maintenance of pools, spas, vehicles and many other applications.
- the adhesion promoter has a number of advantages, particularly the ability to coat or pre-treat a substrate, such as a ceramic (e.g., concrete), metal or polymeric substrate, with the liquid ester/resin adhesion promoter for increased adherence of a sealant composition to the substrate.
- a substrate such as a ceramic (e.g., concrete), metal or polymeric substrate
- Examples include 1,6-hexanediol diglycidyl ether; bisphenol A diglycidyl ether; neopentyl glycol diglycidyl ether; 1,4 butanediol diglycidyl ether; cyclohexanedimethanol diglydidyl ether; polypropylene glycol diglycidyl ether; polyethyleneglycol diglycidyl ether; dibromoneopentyl glycol diglycidyl ether; trimethylopropane triglycidyl ether; castor oil triglycidyl ether; propoxylated glycerin triglycidyl ether; and sorbitol polyglycidyl ether.
- Aliphatic, straight chain epoxides have a general structural formula as follows:
- Cycloaliphatic epoxides such as 1,2-cyclohexene oxide, 1,2-cyclopentene oxide, 1,2,3,4,-diepoxybutene, vinylcyclohexene dioxide, and the like, as well as those products marketed by Shell Oil under the brand name EPON ® , an example of which is shown below.
- Glycidyl esters generally have a structural formula as follows:
- R can also be contain one or more olefmic bonds.
- R can also be aromatic, i.e., -phenyl or -toluyl.
- Examples include glycidyl neodecanoate; acetic acid glycidyl ester; butyric acid glycidyl ester; propionic acid glycidyl ester; valeric acid glycidyl ester; caproic acid glycidyl ester; capric acid glycidyl ester; caprylic acid glycidyl ester; lauric acid glycidyl ester; and glycidyl ester of linoleic acid or of linolenic acid.
- Diglycidyl esters generally have a structural formula as follows:
- R is straight chain aliphatic -(CH 2 ) n wherein n is typically between 1 and 8, or branched aliphatic, or aliphatic/cycloaliphatic mixed, or aliphatic containing one or more olefmic bonds. R can also be aromatic.
- diglycidyl esters include reaction products of glycidol with dicarboxylic acids such as malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and one or more dimer acids.
- the masterbatch polymer and the initial polymeric component of the sealant to which the masterbatch polymer is added are miscible.
- the masterbatch polymer and the initial polymeric component of the sealant are the same.
- the adhesion promoter systems are generally used in an amount between about 0.2% by weight and about 30% by weight, based on the weight of the sealant(s) in the sealant composition(s).
- the long chain esters may be monoesters, diesters, triesters, or mixtures thereof, that may include saturated or unsaturated hydrocarbon chains, straight chain or branched, having none, one, two or three double bonds in the hydrocarbon chains.
- the monoesters have a formula I, as follows:
- R 1 is a C -C 4 alkyl, preferably C 3 -C 18 alkyl, more preferably C 6 -C 18 alkyl, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and,
- R is a C 3 -C 24 hydrocarbon, preferably C 6 -C 24 hydrocarbon, more preferably C 8 -C 18 hydrocarbon, saturated or unsaturated having 1 to 6, preferably 1 to 3 carbon-to-carbon double bonds.
- the diesters have a formula II or LU, as follows:
- R 4 -O-C-(CH 2 ) n -C-O-R 3 (II) wherein n 3-24, preferably 6-18, and more preferably 3-10, and R 3 and R 4 , same or different, are C 3 -C 4 alkyl, preferably C 3 -C 18 alkyl, more preferably C 6 -C 18 alkyl, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds.
- R 5 and R 7 are C 3 -C 24 alkyl, preferably C 6 -C 24 allcyl, more preferably C 8 -C 18 alkyl, straight chain or branched, either saturated or containing 1 to 6, preferably 1 to 3 carbon-to-carbon double bonds;
- R 6 and R 8 are C 3 -C 24 alkyl, preferably C 3 -C 18 alkyl, more preferably C 6 -C 18 alkyl, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds;
- R 10 and R 11 are C 3 -C 4 saturated hydrocarbon chains, preferably C 3 -C 18 saturated hydrocarbon chains, more preferably C 6 -C 18 saturated hydrocarbon chains, straight chain or branched; or unsaturated C 3 -C 24 hydrocarbon chains, preferably C 3 -C 18 unsaturated hydrocarbon chains, more preferably C 6 -C 18 unsaturated hydrocarbon chains, straight chain or branched, containing 1 to 6, preferably 1 to 3 carbon-to-carbon double bonds.
- the triesters have a formula IN, as follows:
- R 12 , R 14 and R 18 are C 3 -C 24 alkyl, preferably C 6 -C 24 alkyl, more preferably C 8 -C 18 allcyl, straight chain or branched, either saturated or containing 1 to 6, preferably 1 to 3 carbon-to-carbon double bonds;
- R 13 , R 15 and R 19 are C 3 -C 4 allcyl, preferably C 3 -C 18 alkyl, more preferably C 6 -C 18 alkyl, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and
- R 16 , R 17 and R 20 are C 3 -C 24 saturated hydrocarbon chains, preferably C 3 -C 18 saturated hydrocarbon chains, more preferably C 6 -C 18 saturated hydrocarbon chains, straight chain or branched; or unsaturated C 3 -C 24 hydrocarbon chains, preferably C 3 -C 18 unsaturated hydrocarbon chains, more preferably C 6 -C 18 unsaturated hydrocarbon chains, straight chain or branched, containing 1 to 6, preferably 1 to 3 carbon-to-carbon double bonds.
- the fatty acid residues or hydrocarbon chains R 2 , R 5 , R 7 , R 12 , R 14 and R 18 of the esters of formulas I, II, III, and IN can be.
- Examples are the hydrocarbon chain residues from the following fatty acids, where the number in parentheses indicates the number of carbon atoms, and the number of double bonds, e.g. , (C 24-6 ) indicates a hydrocarbon chain having 24 carbon atoms and 6 double bonds: Hexanoic (C 6-0 ); Octanoic (C 8-0 ); Decanoic (C 10-0 ); Dodecanoic (C 12- o); 9-Dodecenoic (CIS) (C 12-1 ); Tetradecanoic (C 14-0 ); 9-Tetradecenoic (CIS) (C 14-1 ); Hexadecanoic (CIS) (C 16-0 ); 9-Hexadecenoic (CIS) (C 16-1 ); Octadecanoic (C 18-0 ); 9-Octadecenoic (CIS) (C 18-1 ); 9-Octadecenoic, 12-Hydroxy-(CIS) (C 18-2 ); 9, 12- Octadeca
- Useful cyclic diesters falling within formula III include dimerate ester structures formed by the reaction of a C 36 dimer acid derived from tall oil fatty acids and C -C 24 , preferably C 3 -C 18 , more preferably C 6 -C 18 alcohol, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds.
- Examples of such cyclic esters include the following structures, wherein the dimer acid corresponding to structure A is formed by self reaction of linoleic acid, the dimer acid corresponding to structure B is formed by reacting linoleic acid with oleic acid, and the dimer acid corresponding to structure C is formed by reacting linoleic acid with linolenic acid:
- each R, same or different, in formulas (A), (B), and (C) is a C 3 -C 24 alkyl, preferably C 3 -C 18 alkyl, more preferably C 6 -C 18 alkyl, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds.
- Another example of a useful unsaturated diester is formed by the reaction of a predominantly C 36 dimer acid reacted with 2-ethylhexyl alcohol.
- An additional useful unsaturated diester (dimerate ester) is formed by the reaction of a predominantly C 6 dimer acid with tridecyl alcohol.
- a representative example of the triester (trimerate ester) of formula IN is the following structure (D):
- each R 1 , R 2 , and R 3 is a C 3 -C 24 radical, preferably C 3 -C 18 , more preferably C 6 -C 18 , straight chain, or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds.
- a particularly useful blend of long chain esters is formed from blends of mono, dimer, and trimer acids, for example, products having CAS# 61788-89-4.
- Blends of useful polybasic acids that can be reacted with C -C 24 , preferably C 3 -C 18 , more preferably C 6 -C 18 alcohols, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds to produce the dimerate and trimerate esters, as blends, include the following: EMPOL ® 1010 Dimer Acid; EMPOL ® 1014 Dimer Acid; EMPOL ® 1016 Dimer Acid; EMPOL ® 1018 Dimer Acid; EMPOL ® 1022 Dimer Acid; EMPOL ® 1024 Dimer Acid; EMPOL ® 1040 Trimer Acid; EMPOL ® 1041 Trimer Acid; EMPOL ® 1052 Polybasic Acid; and similar PPJPOLTM products from Uniqema as well as UNTDYME ® products from Arizona Chemical.
- Particularly useful long chain ester additives are made by reacting any of the long chain mono, dimer and/or trimer acids with one or more straight chain or branched C 3 - C 24 , preferably C 3 -C 18 , more preferably C 6 -C 18 alcohols to produce the esters of formulas I, ⁇ , III and IN.
- the above dimer, trimer, and polybasic acids are produced by dimerizing, trimerizing, and polymerizing (oligomerizing) long chain carboxylic acids, particularly from the above-mentioned tall oil fatty acids.
- Tall oil fatty acids are often mixtures.
- the dimer acid produced by dimerizing a C 18 carboxylic acid typically, a mixture of stearic, oleic, linoleic, and linolenic
- a C 18 carboxylic acid typically, a mixture of stearic, oleic, linoleic, and linolenic
- the dimer acid produced by dimerizing a C 18 carboxylic acid typically, a mixture of stearic, oleic, linoleic, and linolenic
- the dimer acid produced by dimerizing a C 18 carboxylic acid typically, a mixture of stearic, oleic, linoleic, and linolenic
- the dimer acid produced by dimerizing a C 18 carboxylic acid typically, a mixture of stearic, oleic, linoleic, and linolenic
- the dimer acid produced by dimerizing a C 18 carboxylic acid typically
- any one, or any blend, of the esters of formulas I, II, III and/or IN, when combined with an adhesive resin, will function to increase the adhesion of a sealant composition in accordance with the invention to substrates such as ceramic substrates (e.g., concrete), glass substrates, metal substrates such as metal flat stock materials, polymeric substrates including substrates comprising natural and/or synthetic rubbers and substrates comprising thermoplastic polymeric materials.
- substrates such as ceramic substrates (e.g., concrete), glass substrates, metal substrates such as metal flat stock materials, polymeric substrates including substrates comprising natural and/or synthetic rubbers and substrates comprising thermoplastic polymeric materials.
- Ceramic substrates include silicon, silicon oxide, and/or complex compounds conventionally known as silicates.
- Suitable substrates comprising synthetic rubbers include homopolymers of conjugated diene compounds, such as isoprene, butadiene, chloroprene and the like, for example, polyisoprene rubber (IR), polybutadiene rubber (BR), polychloroprene rubber and the like; copolymers of the above described conjugated diene compounds with vinyl compounds, such as styrene, acrylonitrile, vinyl pyridine, acrylic acid, methacrylic acid, alkyl acrylates, allcyl methacrylates and the like, for example, styrene-butadiene copolymeric rubber (SBR), vinylpyridine-butadiene-styrene copolymeric mbber, acrylonitrile-butadiene copolymeric rabber, acrylic acid-butadiene copolymeric rubber, methacrylic acid-butadiene copolymeric mbber, methyl acrylate-butadiene copolymeric
- halides of the above-described various rubbers for example, chlorinated isobutylene-isoprene copolymeric rabber (CI- UR), brominated isobutylene-isoprene copolymeric rabber (Br-ILR), fluorinated polyethylene, and the like are included.
- the adhesion promoters of the invention can be used to adhere sealant compositions to other rubbers. All these rubbers may be kneaded with compounding agents conventionally used for compounding with rabber, for example, fillers, such as carbon black, silica, calcium carbonate, lignin and the like, softening agents, such as mineral oils, vegetable oils, prior to vulcanization and then vulcanized.
- Suitable polymeric substrates include thermosetting resins such as phenol/formaldehyde, melamine/formaldehyde, and the like.
- the adhesion promoters include an adhesive resin, which preferably is a condensation product of a formaldehyde or methylene donor and a formaldehyde or methylene acceptor, either pre-condensed, or condensed in-situ while in the sealant composition.
- methylene donor is intended to mean a compound capable of reacting with a methylene acceptor (such as resorcinol or its equivalent containing a reactive hydroxyl group) and generate the resin outside of the sealant composition, or in- situ.
- methylene donors which are suitable for use in the sealant compositions disclosed herein include melamine, hexamethylenetetramine, hexaethoxymethylmelamine, hexamethoxymethylmelamine, lauryloxymethyl-pyridinium chloride, ethoxy-methylpyridinium chloride, trioxan hexamethoxy-methylmelamine, the hydroxy groups of which may be esterified or partly esterified, and polymers of formaldehyde, such as paraformaldehyde.
- the methylene donors may be N- substituted oxymethylmelamines, of the general formula:
- R 3 , R 4 , R 5 , R 6 and R 7 are individually selected from the group consisting of hydrogen, an alkyl having from 1 to 8 carbon atoms and the group -CH 2 OX.
- N,N',N"-trimethylol-melamine The N-methylol derivatives of melamine are prepared by known methods.
- the amount of methylene donor and methylene acceptor, pre-condensed or condensed in-situ, that are present in the sealant composition may vary. Typically, the amount of pre-condensed methylene donor and methylene acceptor is present will range from about 0.1 wt.% to about 15.0 wt.%; or each can be added separately in an amount of about 1 wt.%) to about 10.0 wt.%, based on the weight of sealant in the sealant composition.
- the amount of each of a methylene donor and methylene acceptor added for in-situ condensation ranges from about 2.0 wt.% to about 8.0 wt.%, based on the weight of sealant in the sealant composition.
- the weight ratio of methylene donor to the methylene acceptor may vary. Generally speaking, the weight ratio will range from about 1:10 to about 10:1. Preferably, the weight ratio ranges from about 1:3 to 3:1.
- Resorcinol-free adhesive resins also are useful in the sealant compositions described herein.
- resorcinol-free adhesive resins and adhesive compounds useful in the adhesion promoter systems include those described in U.S.
- Patent Nos. 5,891,938 and 5,298,539 both hereby incorporated by reference.
- the '938 patent discloses a self-condensing alkylated triazine resin having high imino and/or methylol functionality.
- U.S. Patent No. 5,298,539 discloses additives which are substituted derivatives based on cyclic nitrogen compounds such as melamine, acetoguanamine, cyclohexylguanamine, benzoguanamine, and similar alkyl, aryl or aralkyl substituted melamines, glycoluril and oligomers of these compounds.
- the adhesive resins and adhesive compounds which are useful as the adhesive resins in the sealant compositions described herein include the following: adhesive resins selected from the group consisting of derivatives of melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine and glycoluril monomers and oligomers of these monomers, which have been substituted on average at two or more positions on the monomer or on each unit of the oligomer with vinyl terminated radicals, the sealant composition being free of resorcinol; and, these derivatives which have been further substituted on average at one or more positions with a radical which comprises carbamymiethyl or amidomethyl.
- the adhesive resin can be any of the compounds of the following formulas:
- R 4 is a Ci-C 18 alkyl, alicyclic, hydroxyalkyl, alkoxyalkyl or aromatic radical, and in the oligomers, P is 2 to about 10, and L is methylene or the radical — CH 2 — O— CH 2 — .
- These adhesive compounds are particularly useful, wherein on average at least one R 1 in each monomer or in each oligomerized unit is — H — C(O) — OR 4 , particularly the compounds of the following formulas:
- adhesive resins and compounds can include additional additives, particularly those selected from hydroxymethylated and alkoxymethylated (alkoxy having 1-5 carbon atoms) derivatives of melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine and glycoluril and their oligomers.
- Additional adhesive resins useful in the sealant compositions described herein include self-condensing alkylated triazine resins selected from the group consisting of (i), (ii), and (iii): (i) a self-condensing alkylated triazine resin having at least one of imino or methylol functionality and represented by the formula (I)
- adhesive resins are particularly useful wherein at least one R group is hydrogen and/or wherein at least one R 1 group is a lower alkyl group having 1 to 6 carbon atoms, particularly where the adhesive resin is a derivative of melamine, benzoguanamine, cyclohexylguanamine, or acetoguanamine, or an oligomer thereof.
- One particularly useful alkylated triazine adhesive resin of the above formula is wherein Z is -N(R)(CH 2 OR 1 ).
- Another manner of eliminating resorcinol in an adhesive resin for sealant compositions disclosed herein, is to use N-(substituted oxymethyl)melamine and at least one of - or ⁇ -naphthol.
- This adhesive resin employs the monohydric phenols, - or ⁇ - naphthol, as methylene acceptors in the resin forming reaction in the absence of resorcinol.
- Other adhesive resins useful in the sealant compositions described herein include special latices such as, for example, a vinyl-pyridine latex (NP latex) which is a copolymer of about 70 wt.% butadiene, about 15 wt.% styrene and about 15 wt.% 2- vinylpyridine; acrylonitrile rabber latices; and styrene-butadiene rabber latices. These can be used as such or in combination with one another.
- NP latex vinyl-pyridine latex
- Another suitable adhesive resin useful herein, particularly for polyesters, are those which are applied in multi-stage processes, for instance a blocked isocyanate being applied in combination with polyepoxide and the material then being treated using customary resorcinol-formaldehyde resins (RFL dip).
- Additional useful adhesive resins include combinations of RFL dips with other adhesion-promoting substances such as, for example, a reaction product of triallyl cyanurate, resorcinol and formaldehyde or p-chlorophenol, resorcinol and formaldehyde.
- Suitable adhesive resins include polyurethane resins, epoxy resins, phenol aldehyde resins, polyhydric phenol aldehyde resins, phenol furfural resins, xylene aldehyde resins, urea formaldehyde resins, melamine formaldehyde resins, alkyd resins, polyester resins, and the like.
- sealant compositions described herein are characterized in that the surfaces of the sealant compositions are improved to provide a high adhering ability to various substrates.
- the sealants and sealant compositions described herein can be compounded by methods generally known, such as mixing the sealants and/or sealant compositions with various commonly used additive materials such as, for example, processing additives, such as oils, resins including tackifying resins and plasticizers, fillers, pigments, fatty acids, waxes and antioxidants.
- processing additives such as oils, resins including tackifying resins and plasticizers, fillers, pigments, fatty acids, waxes and antioxidants.
- the sealant compositions of the invention can be used in numerous applications, including bonding concrete dividers, e.g., a composite stracture including first and second concrete dividers, and a sealant composition in accordance with the invention therebetween.
- adhesion promoters described herein are very effective in promoting bonding between sealant compositions and concrete substrates, where conventional adhesive pretreatment has been largely ineffective.
- the adhesion promoter systems can be used to provide unexpectedly strong binding between a silicone sealant composition in accordance with the invention and a concrete substrate.
- the invention may be better understood by reference to the following examples in which parts and percentages are by weight unless otherwise indicated.
- Table I compares the effectiveness of sealant compositions in accordance with the invention (i.e., including adhesion promoter systems, here the exemplified adhesion promoter systems comprise dimerate esters) in promoting adhesion to various substrates with conventional sealants.
- Adhesion was examined under the following conditions: (1) dry; (2) after 7 days immersion in water at 50°C; and (3) after 17 days immersion in water at 50°C.
- the sealant compositions were investigated according to the following protocol: (1) "control” indicates that no adhesion promoter in accordance with the invention was added to the conventionally known sealant; (2) “primed” indicates that the substrate was primed (or coated) with a liquid adhesion promoter system ("APS") prior to application of the sealant (e.g., 85% APS, 15% 2-EH, e.g., RX-13928); (3) “resin on silica” indicates that the APS was mixed with a silica support (e.g., RX-13946) and added to provide a sealant composition as a powder; (4) "resin only” indicates that a liquid APS (85% APS, 15% 2- EH, e.g., RX-13928) was added to provide the sealant composition; and, (5) "heat activated resin on silica”
- the APS was applied with a cotton ball and wiped to remove excess of primer.
- the primer system e.g., APS in 2-ethylhexanol
- APS/2-ethylhexanol or APS/silica into the various sealants was accomplished using a double centrifugal mixer (Flacktek, Inc., North Carolina). 90 grams of the total mixture (sealant + APS) was used for each ran and the 90 grams was mixed at least three times for about 30 seconds each time. In all such cases, the shear forces caused the sealant mixture to become warm-to-hot. After mixing, the cap of the mixing container was removed and a plastic film was pushed down onto the sealant surface to protect it from moisture and air present in the head space. The cap was then placed back on the container and the mixture was allowed to equilibrate for at least one day before it was applied to a substrate. The substrates were all one inch wide by three inches long.
- active APS indicates that the APS content has been adjusted for solvent content and/or carrier (e.g., silica) content.
- solvent content and/or carrier e.g., silica
- the results demonstrate a significant improvement in the adhesion of the exemplified silicone-based, urethane-based, and acrylic-based sealant compositions to various substrates, particularly to concrete after 17 days immersion in water at 50°C.
- Table N is a summary of the solvent solubilities of a representative adhesive resin, melamine (Resimene 3520) and a representative ester, RX-13804 (di-2-ethylhexyl dimerate) for use in selecting solvents capable of solubilizing both the ester and the resin in making a liquid solution of the adhesion promoter.
- the solubilities were only determined at 1:1 mixtures of solvent to dimerate/melamine. If both the samples were soluble in the solvent, the solutions were again mixed at a 1:1 ratio of dimerate + solvent to Melamine + solvent.
- the samples provide complete solubility of both dimerate ester and Melamine resin so long as the composition is at a 13% by weight or greater percent solvent level.
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CN102336879A (en) * | 2011-07-01 | 2012-02-01 | 福建利豪电子科技股份有限公司 | Fabrication method for phenolic resin used for paper copper cladded laminate |
WO2012080163A3 (en) * | 2010-12-13 | 2012-10-18 | Dsm Ip Assets B.V. | Polymer composition containing a polymer, which polymer contains monomer units of a dimerised fatty acid |
WO2013086014A1 (en) * | 2011-12-07 | 2013-06-13 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Vegetable oil-based pressure-sensitive adhesives |
EP2920279A4 (en) * | 2012-11-19 | 2016-05-25 | Biosynthetic Technologies Llc | Diels alder based estolide and lubricant compositions |
US9453151B2 (en) | 2012-04-09 | 2016-09-27 | Avery Dennison Corporation | Pressure sensitive adhesives based on renewable resources, UV curing and related methods |
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EP1304210A1 (en) * | 2001-10-19 | 2003-04-23 | Byk-Chemie GmbH | Processing aid for the conversion of plastics |
WO2003095550A1 (en) * | 2002-05-09 | 2003-11-20 | The C.P. Hall Company | Adhesion promoter for cord-reinforced rubber and metal or polymer substrate/rubber composites |
-
2003
- 2003-11-19 WO PCT/US2003/036990 patent/WO2005061646A1/en not_active Application Discontinuation
- 2003-11-19 AU AU2003295660A patent/AU2003295660A1/en not_active Abandoned
- 2003-11-19 EP EP03786860A patent/EP1704196A1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0450105A1 (en) * | 1990-03-29 | 1991-10-09 | Adco Products, Inc. | Room-temperature, moisture-curable, primerless, poluyrethane-based adhesive composition and method |
EP1304210A1 (en) * | 2001-10-19 | 2003-04-23 | Byk-Chemie GmbH | Processing aid for the conversion of plastics |
WO2003095550A1 (en) * | 2002-05-09 | 2003-11-20 | The C.P. Hall Company | Adhesion promoter for cord-reinforced rubber and metal or polymer substrate/rubber composites |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012080163A3 (en) * | 2010-12-13 | 2012-10-18 | Dsm Ip Assets B.V. | Polymer composition containing a polymer, which polymer contains monomer units of a dimerised fatty acid |
CN102336879A (en) * | 2011-07-01 | 2012-02-01 | 福建利豪电子科技股份有限公司 | Fabrication method for phenolic resin used for paper copper cladded laminate |
CN102336879B (en) * | 2011-07-01 | 2012-10-03 | 福建利豪电子科技股份有限公司 | Fabrication method for phenolic resin used for paper copper cladded laminate |
WO2013086014A1 (en) * | 2011-12-07 | 2013-06-13 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Vegetable oil-based pressure-sensitive adhesives |
CN104105770A (en) * | 2011-12-07 | 2014-10-15 | 由俄勒冈州高等教育管理委员会代表的俄勒冈州立大学 | Vegetable oil-based pressure-sensitive adhesives |
CN104105770B (en) * | 2011-12-07 | 2016-04-06 | 由俄勒冈州高等教育管理委员会代表的俄勒冈州立大学 | Plant oil based pressure sensitive adhesive |
US9556368B2 (en) | 2011-12-07 | 2017-01-31 | Oregon State University | Vegetable oil-based pressure-sensitive adhesives |
RU2629084C2 (en) * | 2011-12-07 | 2017-08-24 | Орегон Стейт Юниверсити | Adhesives, gluing while pressing on the basis of vegetable oil |
US9453151B2 (en) | 2012-04-09 | 2016-09-27 | Avery Dennison Corporation | Pressure sensitive adhesives based on renewable resources, UV curing and related methods |
EP2920279A4 (en) * | 2012-11-19 | 2016-05-25 | Biosynthetic Technologies Llc | Diels alder based estolide and lubricant compositions |
Also Published As
Publication number | Publication date |
---|---|
EP1704196A1 (en) | 2006-09-27 |
AU2003295660A1 (en) | 2005-07-14 |
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